Detergent composition



Patented Mar. 12, 1946 DETERGENT COMPOSITION Otto Lind, Dusseldorf, Germany, assignor, by mesne assignments, to The Procter & Gamble gilillinpany, Cincinnati, Ohio, a corporation of No Drawing. Application November 10, 1934, Se-

rial No. 752,462. 1933 4 Claims.

This invention relates to compositions having exceedingly high cleansing powers and other valuable properties rendering them suitable for many purposes in the arts. Such compositions broadly considered are composed of or contain principally as one component any one or number of diverse classes oi! lime-resistant, capillarily-active compounds which in common contain in their molecules at least one higher aliphatic radical having at least 8 carbon atoms and at least one substantially terminal radical, i. e., terminal or almost terminal radical, adapted to efl'ect or increase the water-solubility of the compound, and as a second component any one or more of a number of water-soluble salts of those phosphoric acids which are, or which may be considered to be produced from ortho-phosphoric acid by the removal of water. To impart special properties, additional agents may be incorporated in the compositions, as hereinafter explained in more detail.

Anobject of the present invention is to produce cleansing compositions having superior properties to compounds or compositions now available on the market.

Another object is to improve the stability and other properties of so-called lime-resistant oranic detergent and wetting agents.

One specific object is to provide compositions of matter having exceedingly rapid and high cleansing properties composed of water-soluble salts of inorganic polybasic oxygen acid esters of higher molecular alcohols together with water-soluble salts of phosphoric acids poorer in water than ortho-phosphoric acid.

Another specific object is to provide compositions composed of water-soluble salts of the abovementioned phosphoric acids in admixture with those alkali metal or other salts of such inorganic polybasic acid esters of others which contain one or more alkyl radicals having 8 or more carbon atoms in the molecule.

Another specific object is to provide compositions composed of water-soluble salts of the above phosphoric acids an admixture with water-soluble salts of sulfuric and other acid esters of carboxylic acid esters containing in the molecule one or more alkyl and/or acyl radicals having at least 8 carbon atoms.

Another specific object is to produce from allphatic hydrocarbons having at least 8 carbon atoms in the molecule a series 01' highly effective cleansing agents, such agents being composed of water-soluble salts of certain inorganic polybasic oxygen acid esters of such hydrocarbons together In Germany November 15,

with any one or more or the hereinbeiore mentioned phosphate salts.

Other specific objects are toprovide efilcient cleansing agents from compounds containing at least one higher aliphatic radical having 8 or more carbon atoms in the molecule, which have been esterified with any one or more of certain acids or acid substances or instead have been reacted with any one or more of certain non-acid substances adapted to effect or increase the solubility of the higher aliphatic compounds, such acids or substances including:

1. Thiosulfuric acid. 2. The phosphoric acids.

3. Sulfuric acids (forming sulfuric acid esters or sulionic acid derivatives).

. Sulfinic acid.

. Phosphoric acid.

. Quaternary ammonium compounds.

. Radicals containing a plurality oi hydroxy groups.

. Radicals containing a plurality of ether groups.

Another specific object is the production oi cleansing and wetting compositions by the use oi alkali metal or other water-soluble salts oi pyrophosphoric acid, especially neutral alkali metal pyro-phosphates together with lime-resistant, capillarily-active compounds containing at least one higher aliphatic radical having at least 8 carbon atoms and also a substantially terminal radical adapted to effect or increase the solubility of the compound.

Another specific object is to produce compositions of valuable properties composed of watersoluble salts of certain polyphosphates in admixture with such lime-resistant compounds as broadly described above.

Another specific object is to provide compositions having excellent cleansing properties by admixing alkali metal or other soluble salts of metaphosphoric acid or of a polymer of such acid with a lime-resistant compound as described above.

Other objects and advantages will ap ear from the detailed description hereinafter set out.

The term higher aliphatic radicals" is used herein to describe radicals of higher fatty alcohols having at least 8 carbon atoms in the molecule and also radicals of higher fatty acids having at least 8 carbon atoms in the molecule. The radicals may be those having a straight chain as well as the equivalent cyclo-aliphatic radicals having similar properties, for example, the radicals of the naphthenic acids and resin acids, and

also those of the corresponding alcohols. The higher aliphatic radical may be combined directly to the radical which effects or increases watersolubility of the compound or' indirectly through oxygen, sulfur or nitrogen atoms, or through alkyl or acyl radicals or through various combinations of such atoms and radicals.

The various classes of compounds in accordance with the present invention-which may contain the higher aliphatic radical or radicals comprise alcohols, hydrocarbons, ethers, esters, mixed ethers and estersf sulfones and other classes, all heresalt. Additional radicals which are satisfactoryfor this purpose are the polyoxy and/or polyether groups.

In forming the salts of the above mentioned radicals adapted to improve the water-solubility, alkalies such as sodium and potassium are preferably employed. However, ammonia and also organic amines such as the pyridines and their homologues and triethanolamine may also be used to advantage to produce products of special properties. When the quaternary ammonium compounds are employed to affect the water-solubility, use is made ,of their salts formed by reaction with acids such as hydrochloric acid, sulfuric acid, phosphoric acid and the like.

One group of compounds which, when mixed with a water-soluble salt of a phosphoric acid poorer in water than ortho-phosphoric acid, form compositions possessing excellent cleansing and wetting properties comprise higher ali hatic a1- cohols rendered water-soluble by the various acids or other a ents herein disc osed. Exam les of such alcohol derivatives include the alkali metal salts of the sulfuric acid esters of higher fatty alcohols having at least 8 carbon atoms in the molecule, such as the sodium salts of the sulfuric acid esters of octylic alcohol of decylic alcohol, of dodecyl c alcohol. of tetradecylic alcohol, of hexadecylic alcohol. of octadecylic a cohol, of oleyl alcohol. of rincinoleyl alcohol. and of mixtures of the same in any desired propo tions. Since t ese alcohols are at present most easily obtained from natural oils, fats and liquid waxes, the hydroxy radical occurs at t e end of the alkyl chain. Hence the sulfuric acid or other radical adapted to affect t e water-solubility joins in a terminal position. However, in the treatment of unsaturated or hydroxy alcohols an additional sulfuric acid or other acid group may be joined on the side of the chain and compositions produced therefrom constitute another phase of the present invention; Insteadof the sulfuric acid esters or the enumerated alcohols, there ma be used the phosphoric acid esters and the thiosulfuric acid esters in the form of their watersoluble salts. 5'

Compositions of valuable properties may be made from the paraffin hydrocarbons as well as from the alcohols. As examples of hydrocarbon derivatives there may be mentioned the watersoluble salts of octaine alpha sulfonic acid, decane aseaa'ze however, that the sulfonic or other acid radical be joined at the terminal carbon atom for satisfactory compounds may be made by a reaction in which the sulfonic or other group joins at a carbon atom near the terminal carbon atom. The sulfonic or other acid derivatives may be derived from certain unsaturated hydrocarbons. Other hydrocarbon derivatives include the salts of the alpha sulfonic acids of fatty acids, such as the disodium salt of palmitic-acid-alpha-sulfonic acid.

Compositions having very excellent cleansing and other properties may also be made from certain ethers and from certain esters which contain in their molecules higher aliphatic residues containing at least 8 carbon atoms. Examples of such compounds are the hydroxy alkyl sulfonic acids, such as beta-hydroxyethane-sulfonic acid, which are etherlfied at the hydroxy group by higher alkyl radicals or esterified by higher acyl radicals of the nature hereinbefore described.

Other examples of such ether compounds are the sodium salts of beta-oct-yl oxyethane-sulfonic acid, of beta-decyl-oxyethane sulfonic acid, of beta-dodecyl oxyethane-sulfonic acid, of betatetradecyl-oxyethane-sulfonic acid, of beta-hexadecyl oxyethane-sulfonic acid, of beta-octadecyl oxyethane-sulfonic acid, as Well as mixtures of the same and their homologues.

Other suitable ether derivatives from which valuable cleansing compositions may be made by compounding with salts of those phosphoric acids which are poorer in water than ortho-phosphoric acid are the salts of the sulfuric acid esters, phosphoric acid esters and thiosulfuric acid esters of those mono or poly glycols and glycerols which are partially etherified by higher alkyl radicals. Such compounds are, for example, the salts of the sulfuric acid esters of glycerol mono-octyl ether, g ycerol monodecyl ether, glycerol monododecyl ether, glycerol monotetradecyl ether, glycerol monohexadecyl ether, glycerol mono-octadecyl ether and mixtures of the same in any desired proportions. Very satisfactory results may be obtained also by the use of salts of the sulfuric acid esters of glycols, poly-g ycols and poly-glvcerol ethers which correspond to the above mentioned glycerol ethers. Instead of using the ethers, similar esters may be employed, in which case the acid esters of the various glycols and glycerols are esterified by reaction with higher fatty acids or res n acids or naphthenic acids, for example, salts of the glycerol mono fatty acid esters such as lauric acid monoglyceride, palmitic acid monoglyceride and stearic acid monoglyceride.

Other ester compounds suitable for the production of the compounds of the present invention are the salts of the higher alkyl esters of the sulfocarboxylic acids such as sulfoacetic acid, sulfopropionic acid and their homologues. Such salts are, for examplathe sodium salts of sulfoacetic acid which have been esterified with an octyl. decyl, dodecyl, tetradecyl, hexadecyl or an octadecyl radical.

Mixed ethers and esters serve very satisfactorily as bases for the production of suitable compounds. The sulfuric acid, phosphoric acid and thiosuli'uric acid esters of low aliphatic oxycarboxylic acids which are esterified by higher aliphatic or cyclo-aliphatic alcohols produce excellent compositions. As example of such comassume pounds, mentionmay be made of the alkali salts of the sulfonation products of the hydroxy-ethoxy-acetic acid which have been esterified with any one ofthe higher alkyl radicals, namely, the octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl radicals. The ester-like union of the higher aliphatic or cyclo-aliphatic radical with the alkyl radical containing. the ground adapted to increase the water-solubility maybe replaced by the amido union such as the carboxylic amide union or the sulfone-amide union. The etheric union of the higher aliphatic or cyclo-aliphatic radical with the alkyl radical carrying the group affecting the water-solubilitymaybe replaced by the sulfide union or the amine union.

The salts of those carboxylic acids which are resistant to lime and which contain in the molecule an aliphatic or cyclo-aliphatic radical will form valuable compositions in accordance with the present invention when mixed with any one of the phosphate compounds hereinafter described in more detail. Salts of such carboxylic acids are, for example, the water soluble salts of acetic acid into which there has been substituted a higher alkoxy or an alkyl-mercapto radical such as any of the following: octyl oxy, decyl oxy, dodecyl oxy, tetradecyl oxy, hexadecyl oxy and octadecyl oxy radicals or octy1-mercapto-, decylmercapto, dodecyl-mercapto; tetradecyl-mercapto, hexadecyl-mercapto, and octadecyl-mercapto radicals. Another specific example of a suitable compound is the sodium salt of the semi-lateral thiodiglycolic acid-n-octyl ester.

Suitable compositions may also be made with various sulfone compounds as bases for the higher alkyl radicals. The salts oi. the sulfuric acid esters, phosphoric acid esters and thiosulfuric acid esters of those sulfones which on the one hand contain a higher alkyl radical such as an octyl, decyl, dodecyl, tetradecyl and hexadecyl radicals and on the other hand a low aliphatic radical containing at least one hydroxyl group, such as the hydroxy ethyl radical and the betagamma dihydroxy propyl radical, are examples.

Compositions having special properties may be made from the carbonic acid esters and urethanes which on the one hand are substituted by a higher the water-solubility oi. the compound.

When use is made of a quaternary ammonium radical or an amine group neutralized by reaction with an acid for efiecting or increasing the water-solubility of the higher aliphatic radical containing compound, the addition of alkaline salts is avoided. Water-solubility may be imparted to such compounds b other radicals such as those which contain a plurality of hydroxy groups and/ or ether groups. When such hydroxy or ether groups are employed suitable compounds are produced by the reaction of a considerable amount of an alkalene oxide such as ethylene oxide, glycide. epichlorohydrin, and the like. upon higher alcohols, such as octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl alcohols and their mixtures, as well as upon fatty acids such as lauric acid and stearic acid. The sugar alcohols in the form of their reaction products with the above mentioned alkalene oxides which have been partially etherified by higher alkyls or partially esterifled by higher fatty acids are also suitable forthe production of the compounds of the present invention.

The water-soluble salts of the phosphoric acids poorer in water than ortho-phosphoric acid which are used in compounding the compositions or the present invention include the alkali metal salts of pyro-phosphoric acid, particularly neutral alkali metal pyro-phosphates, suitable salts being sodium acid Pym-phosphate, neutral sodium pyro-phosphate and potassium pyro-phosphate. Compositions suitable for the same or for diil'erent purposes may be made with other phosphates such as the alkali metal meta-phosphates as sodium and potassium meta-phosphates or Jpolymeric forms of such phosphates. Particularly valuable are the" compositions derived by the use of poly-phosphates, for example, those having the formula, NatPaomand NasPiom. Instead of using the alkali metal salts of the above mentioned phosphates, the ammonium salts may be employed. For specific purposes it is often advantageous to use mixtures of these phosphate salts.

The compositions of the present invention contain many valuable properties not had by the higher aliphatic radical containing compounds when used alone or in the absence of the above mentioned pyro and other phosphates. Thepresence of such phosphate salts produces uniformity in the rate of the higher alkyl compound in going into solution in water. The higher alkyl compounds have increased solubility and also an increased velocity of solution. The compositions of the invention have a greater foaming capacity in aqueous solution than the higher alkyl compounds alone and furthermore, are more stable toward alkaline earth and heavy metal salts which are present in hard water.

The compositions hereinbefore described may be supplemented by other substances which impart valuable properties and produce compositions suitable for special purposes. Known agents for wetting, washing, purifying, emulsitying and dispersing, or mixtures thereof when added to the compositions produce compositions of considerable value. Compositions of somewhat different properties maybe formed by incorporating alkali compounds such as soda ash, water glass, borax and/or such compounds as the perborates, persulfates and percarbonates, and the like, or neutral agents such as sodium sulfate, or acid agents such, for example, as sodium disulfate, or mixtures of these agents.

The compositions may be manufactured and sold in solid form as a powder or in granular form, or in the form of thin strips. They also may be sold in the form of a solution, dissolved in aqueous or non-aqueous liquids. When the compositions are utilized in the dissolved form for cleansing or other purpose, solutions may be utilized in a warm condition or in a cold condition as the circumstances may require.

The extremely valuable properties of the compositions constituting the present invention may be illustrated by the following comparative experiments: With the use of water of 12 degrees hardness, two solutions are prepared, one of them containing only the sodium salts of the sulfuric acid esters of a mixture of higher fatty alcohols composed of decyl, dodecyl, tetradecyl, hexadecthe solution not containing the same in removing considerably more of the coloring matter from the fabric samples treated. This superior cleansing power is of considerable commercial value.

Samples of the above solutions were permitted Example 3 which when used in accordance with commercial ter of 12 degrees hardness. The results are shown in the following table:

'lenl'old treatment with a solution containing- 3 5? Per cent 1 5 g. cmmuorcin] fatty-alcohol sulionalo per liter 0.9l 2 5 1. commercial fatty-alcohol sulionate 2 2. hora):v l. 08 3 5 1:. commercial fatty-alcohol sulfonate 2 g. di-

sodium phosphate 2. 52% 4 5 g. commercial fatty-alcohol suli'onate 2 g. trisodium phosphate 2. 39 5 5 5:. commercial fatty-alcohol sulionatc 2 g. sodium metaphosphate 0. 54

From this table it may be observed that the ash content of the treated cotton cloth remained very low after treatment with the solution of the compounds of the present invention, whereas, with the other solutions the ash content was almost double or evenmore. The advantages of the compositions of the present invention are clearly apparent and their suitability for numerous commercial processes is obvious.

Similar favorable properties may also be obtained with the other enumerated capillarily active compositions disclosed herein.

Example 1 One hundred parts by weight of a fatty alcohol sulfonate in the form of a paste, containing the sodium salts of the sulfuric acid esters of decyl, dodecyl and tetradecyl alcohol which contained about 65% of the pure sulfonate and about 10% of. inorganic salts were kneaded together with 18 parts of calcined tetrasodium pyrophosphate. The mixture obtained was dried by any suitable apparatus, for example, in a vacuum belt dryer and thereafter was ground to-produce a mass having grades of uniform size. The granular powder obtained constitutes a detergent having a cleansing power much in excess of the fatty alcohol sulfonates in the absence of pyrophosphate.

Example 2 Eighty parts by weight of a commercial fatty alcohol sulfonate mixture in dry form containing the sodium salts of the sulfuric acid esters of octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl alcohols containing 85 to 95% of pure sulfonate is intimately mixed by means of a roller mixer with 20 parts by weight of a finely powdered sodium metaphosphate and thereafter ground into particles of uniform size. In all concentrations in hard waters the compositions thus prepared produce solutions having considerably improved cleansing power and solubility. If in this example a portion of the metaphosphate such as about 10 parts are replaced by calcined tetrasodium'pyrophosphate, then a high-grade washing composition is likewise obtained.

practice results in an excellent cleansing action. Example 4 Eighty .parts by weight of a mixture of substantially pure sodium salts of higher aliphatic sulfonic acids containing predominately the sodium salt of dodecane-sulfonic acid are ground to a homogeneous mass in a ball mill with 10 parts by weight of calcined tetrasodium pyrophosphate or of sodium meta-phosphate. The compositions thus obtained have a considerably greater solubility in hard waters and a superior washing power to the sodium salts of the higher aliphatic sulfonic acids in the absence of such phosphate salts.

Example 5.

One hundred and twenty-five parts by weight of a dry commercial fatty alcohol sulfonate product containing to pure sulfonate are intimately mixed by means of any suitable mixing device with 25 parts by weight of a finely powdered sodium polyphosphate, for example, of the composition of NacP4O1s and thereafter the mixture powdered to produce a granular mass with grains of suitable size. The mass produced possesses a considerably improved cleansing power and solubility.

In the foregoing examples there may be substituted for the fatty alcohol sulfonates other lime-resistant soap substitutes,. for example, aliphatic amino-sulfonic or oxy-sulfonic acids reacted with compounds containing higher fatty acid radicals.

It should be understood that the present invention is not limited to the specific disclosure of the foregoing examples, but that it includes all substances coming within the scope of the broad description of the invention and of the terms of the appended claims.

I claim:

1. A detergent composition comprising essentially a sodium salt of a sulphonated alkyl of the formula aaoaan 5 where R is a radical 01' from 10 to 18 carbon atoms 4. A detergent composition consisting essenand x is an alkali metal and a water soluble salt tlally oi a aultonated alkyl oi the formula of tetraphosphoric acid.

3. A detergent composition compriaingeasentially a sodium salt of a sulfonated alkyl or the 5 formula: v a

o o x m where R is a radical 01' from 10 to 18 carbon atoms 0 o and X stands for an alkali metal or an ammonium radical and a water soluble salt of a polyphoshate, th cu consist of the alkali metal where R is a radical of from 10 to 18 carbon atoms 2 ai i g or gs and mm. and a sodium polyphoaphate, oi the group consistlng of ammo and Name. o-rro, mm 

